Stable diazo compound and process of making same



Patented May 24 1927.

UNITED STATES Parsrrrv orifice.

GUILLAUME DE MCNTMOLLIN AND GERALD BoNHoTE, on BASEL, SWITZERLAND, As'- sIGNoIis To SOCIETY oE CHEMICAL INDUSTRY IN BASLE, or BASEL, SWITZERLAND.

STABLE DIAZO COMPOUND AND PROCESS OF MAKING SAME.

No Drawing. Application filed August 29, 1924, Serial No. 735,042, and in Switzerland September 21, 1923.

The present invention relates to new sta ble diano-compounds appropriate for the production of azo-dyestuli's on the fibre. lt comprises the new products as well as the process of making saine.

1n the specilications of our U. b. Lettersl Patents No. 1,453,660 and No. 1,504,437 the use of. diam-compounds ot' unsulfonated aryl and arallyl ethers of o-aininophenol has been recommended for the production of dyestuil's on the fibre. lt is known, however, that owing to their chemical and physical properties unsulfonated aryl ancharalkyl ethers of o-aminophenols are dillicult to diazotize. The production of the corresponding diam-compounds as described in the examples of the German Patents No. 214,496

and No. 216,642 yields diazo-solutions which ,contain such an excess ot' acid that they have no practical value for the purpose in dicated in our patents mentioned above.

It has now been found that by reacting with sulfonie acids oi the aromatic series not containing hydroxy or amino groups, as for instan'icenicno and polysulfonic acids of naphthalene, on the` above named diazo compounds, same are transformed into remarkably stable derivatives, which may he isolated either by evaporation or by precipitation and be thus brought. on the market in a solid forni.

The new products forni grains, or more or less yellow colored powders. They are very stable, easily soluble in Water to yellow solutions which couple instantly and yield, when in presence of 'an alkaline solution of naphthol and by splitting 0H the Aresidues of the sulfonic aroniatic acids to which they were combined before, red azo-dyestufis. Owing to these properties the new products are most valuable for the commercial production .of dyestus on the textile ibre and their manufacture means an important progress in this branch of industry.

Ewample 1. I

220 parts ol" phenyl other of 4--chloro-2- ainino-l-phenol are diazotized by means of G00 parts oi` hydrochloric acid, 800 parts of ice water and 160 parts of nitrite of sodium, i. e. twice the theoretical quantity required.

:20 parts of the trisodiuni salt oi' naphtha-- lene 1:3:6-trisulfonie acid are then added,

while stirring, until the whole i. well dissolved. The yellow'` solution thus obtained f is filtered troni slight impurities and evaporated in a vacuum, preferably :it ya temperattire not higher than 50 (l. 'lhere is thus obtained a yellow powder havingV properties` as described in the introduction. The product is probably a mixture of thc diazoniuni salts corresponding with the forniulae:

A similar product is obtained if benzyl ether ol' 4-chloro-2-a1nino-Lphenol is used instead ol' the correspon/ding phenyl ether.

Example t.

rates, and the product thus formed is filtered after some time` This new product7 which 1s Amostprobsbly e diezoiuum salt corresponding with the formula.;

Lef/:seco

disulfonic acid and mix it thoroughly with 120 parts of the trisodium Salt of naphtho.- iene-lzflr-trisul'ouic scid. There is thus obtained s yellow powder which is easily soluble-j water.

Ema/mpi@ 270 parts of benzyl other of 4cliloroomino-l-phenoi, suspended in 3000 ports of iced water, are dizizotized by means of 7i' ports of soiliuili nitrite :imi ll) parts of hydrochloric scid. To tbe clear solution there ere added 382 parte of disodium salt of naplitlieleue-f:ilisuliouic scid und the product time obtained, which separates after some time, is' lilteied and dried. lt forms a yellow powder rut-lier easily soluble in wter. The new product is probably a diazouiuzii eelt corresponding with the 'formule.:

220 peri/s of phenyl ether of ichloro2 eminol.plieool ere diszotized as described above and 225 parte of sodium salt of 3 nit"^fbeozeue-sulionie acid ere added to the liltered solution of ,the diem-compound. The product that Separates immediately is iltered and dried. lit is Very probably e diozooium salt. corresponding with the for- WHEN and forms e. yellow powder soluble with diffliculty in Water, more easily iii bol; Water.

Similar products obtained if instead oi? tlie phenyl other of 4-cl1loro-eminopbenol its ciiloeoplienyl9 cresyl7 chlorocrcsyi, naphthyle etbers etc` are employed.

The solubility of sparingly soluble products may be eiilianced by addition of trior higher sulonated acids o 'soplotlielerie5 as lies been disclosed in VIlzmiple 2.

1. The process of making" new stable diezo-con'ipounds, 'which consists in treating disco-derivatives of unsulfonated aryl and arslkyl etliers of o-aminoplienol with sul- -fonic acids o' the aromatic series which do not contain OH or NH2 groups.

2. The process of making new stable di:izocompoureds7 which cousis'c: in treatise diem-derivatives of uosulfomited erfl enel aralliyl eliers o23 o-eminopl'ieiiol with sulonic acids of riephthelene which do not contain OH or NH"2 groups.

The process o making new stable diamo-compounds, which consists in treating dime-derivatives of unsulfoneted aryl and areliryi etbers of oa.minopbenol with a disulfonic acid'of risphtlislene which do not contain @H or NH2 groups, in isolating the product thus obtained and in mixing tile letter with e trisulfonic acid of naphthlene.

4, As new products the stable diem-compounds obtained by the action of sulfonio acids of the aromatic series which do not contain OH or NH2 groups on diazo-deriye tives of iirisulfoneted aryl and orellyl others of oeminophenol, forming more or less yel low colored powders, soluble in Water to yellow solutions :md yielding, it in presence of an alkaline solution of naplithol by splitting off the residues 'of sul'fouated aromatic acids to which Athey were combined before, red ezo-dyestuls- 5. As new products tbe stable diazo-com pounds obtained by the action or" sulfonic acids of nophtlialene which do not contain OH or NH2 gioups'on diam-derivatives of uusulionsed aryl oud aralkyl others of o-sminoplieriol, forming more or less yellow colored powders, soluble in Water to yellow solutions and yielding. if in presence of en alkaline solution of -nspiitliol by splitting oil tbe residues or nephthalene sullioioie acids to 'which they were combined rezagos before, red azo-dyestuls, insoluble in weten 6. As new products the Stable diam-comounds obtained by the action of polysulonic acids of naphthalene which do not con tain OH or NH2 groups on diazo-derivatives of unsulfonated aryl ethers ot' o-ami nophenol, forming more or less yellow colf ored powders, soluble in water to yellow solutions and yielding, if in presence of an alkaline solution of -naphthol by splitting ofi, the residues ofv naplit'nalene polysul ionic acids to which they were combined before, red azo-dyestu's.

7. As new products the stable diazo-compounds obtained by successive action of a disulfonic acidV and a trisulfonic acid of napthalene which do not containv OH or NH2 groups on diasoderivatives of unsulfonated aryl ethers of an o-aminoplnenol,

forming more or less yellow colored pensif-l ders, soluble in water to yellow solutions and yielding, if in presence of 'en alkaline solution of -naphtbol Toy splitting o the residues of naplitlialene diand trisulonic acids to which they were combined before, red azo-dyestulis. l

8. As a new product the stable diazo-compound obtained by successive action of a disulfonic and a trisulfonic acid of naphthalene which do not contain OH or NH2 groups on diam-derivative of the phenyl ether of the -ohloro-Q-amino--l-phenol, forming a yellow colored powder soluble in water to a yellow solution, and yielding, if in presence of an alkaline solution of naphtliol, by splitting 0E the residues of the nap'hthalene sulon-ic acids to which it was combined before, a red azo-dyestu insoluble in water. 1

in witness whereof we have hereunto signed our names this ltli day of August, 1924.

GUILLAUll/m DE MONTMDLLIN.

GERALD eoNHoTsv. 

